Acrylonitrile derivatives as additive for electrolytes in lithium ion batteries

ABSTRACT

An electrolyte composition (A) containing (i) at least one aprotic organic solvent; (ii) at least one conducting salt; (iii) at least one compound of formula (NC)(A 1 X 1 )C═C(X 2 A 2 )(CN) wherein X 1  and X 2  are independently from each other selected from N(R′), P(R 1 ), O, and S, and A 1  and A 2  are selected from H or organic substituents; and electrochemical cells containing electrolyte composition (A).

The present invention relates to an electrolyte composition (A)containing

(i) at least one aprotic organic solvent;

(ii) at least one conducting salt;

(iii) at least one compound of formula (I)

-   -   wherein    -   X¹, X², A¹, and A² are defined below, and        (iv) optionally, at least one further additive.

The present invention further relates to the use of compounds of formula(I) as additives for electrolytes in electrochemical cells and toelectrochemical cells comprising the above described electrolytecomposition (A), at least one cathode (B) comprising at least onecathode active material, and at least one anode (C) comprising at leastone anode active material.

Storing electrical energy is a subject of still growing interest.Efficient storage of electric energy would allow electric energy to begenerated when it is advantageous and used when needed.

Accumulators, for example lead accumulators and nickel-cadmiumaccumulators, have been known for many decades. The known leadaccumulators and nickel-cadmium accumulators have the disadvantages,however, of a comparatively low energy density and of a memory effectwhich reduces the rechargeability and hence the useful life of leadaccumulators and nickel-cadmium accumulators.

Lithium ion accumulators, frequently also referred to as lithium ionbatteries, are used as an alternative. They provide higher energydensities than accumulators based on lead or comparatively noble heavymetals.

Since many lithium ion batteries utilize metallic lithium or lithium inoxidation state 0, or produce it as an intermediate, they are watersensitive. Moreover, the conductive salts used, for example LiFP₆, arewater sensitive during long-term operation. Water is therefore not ausable solvent for the lithium salts used in lithium ion batteries.Instead, organic carbonates, ethers, esters and ionic liquids are usedas sufficiently polar solvents. Most state of the art lithium ionbatteries in general comprise not a single solvent but a solvent mixtureof different organic aprotic solvents.

During charge and discharge of lithium ion batteries various reactionstake place at different cell potentials. It is known that during thefirst charging process of a lithium ion battery usually a film is formedon the anode. This film is often called solid electrolyte interface(SEI). The SEI is permeable for lithium ions and protects theelectrolyte from direct contact with the anode and vice versa. It isformed by reductive decomposition of components of the electrolytecomposition like solvents, e.g. carbonates, esters, and ethers, andconductive salts on the surface of the anode, especially if the anodeactive material is a carbonaceous material like graphite. A certainamount of the lithium from the cathode is irreversibly consumed for theformation of the SEI and cannot be replaced. One possibility to reducethe amount of irreversibly consumed lithium is the addition of suitablechemical compounds which are easily decomposed on the anode by reductionand thereby forming a film on the surface of the anode. One especiallywell suited compound is vinylene carbonate, see for instance EP 0 683587 B1 and U.S. Pat. No. 6,413,678 B1. Vinylene carbonate forms a stableSEI on a graphite anode in lithium ion batteries.

Other film forming additives are known, inter alia acrylonitrile andderivatives thereof. Santner et al., J. Power Sources, 2003, 119 to 121,pages 368 to 372 reports the use of acrylonitrile in propylene carbonateas film forming additive in lithium ion secondary batteries having agraphite anode and LiMn₂O₄ as cathode active material. US2006/0194118 A1discloses electrolyte composition for lithium ion batteries containingat least one first additive capable o forming a chelating complex with atransition metal and being stale at voltages ranging from about 2.5 to4.8 V. Said first additive may be inter alia 1,2-dicyanoethylene or1,2-dicyanobenzene. JP 2012195223 A2 discloses the use of substitutedbenzonitrile derivatives in electrolytes for lithium ion batteries. FromEP 2 120 279 A1 electrolytic solutions for secondary batteriescontaining acrylonitrile derivatives like methacrylonitrile,2-furonitrile, fumaronitrile and tetracyanoethylene are known. U.S. Pat.No. 7,008,728 B2 describes electrolytes for lithium secondary batteriescontaining acrylonitrile or derivatives thereof as additives forming anorganic SEI on the negative electrode during initial charging. US2004/0013946 A1 is directed to non-aqueous electrolytic solutions forlithium batteries containing at least one nitrile compound likeactetonitrile or 1,2-dicyanobenzene and at least on S═O group containingcompound. WO 2012/029386 A1 discloses lithium ion batteries containingacrylonitrile compounds in the electrolyte composition, e.g.2-furonitrile. From US 2011/207000A1 the use of benzonitrilederivatives, in particular of fluorinated benzonitriles as additives inelectrolytes for electrochemical cells is known. JP 2003-086248 Aconcerns electrolytic solutions for secondary batteries containingcompounds having an electrophilic group conjugated with a carbon-carbonunsaturated bond. These compounds may inter alia be selected fromacrylonitrile, methacrylonitrile and 2-cyanoacrylic acid ethyl ester.

Nevertheless there is still the need for enhancing the lifetime ofsecondary batteries and a demand for electrolyte additives leading to aprolonged life time and cycle stability of secondary lithium ionbatteries.

It was an object of the present invention to provide an electrolytecomposition leading to an improved lifetime of lithium ion batteries. Afurther object of the present invention was to provide lithium ionbatteries of high energy density and/or higher operating voltage havinggood performance characteristics and long lifetime.

This object is achieved by an electrolyte composition (A) containing

(i) at least one aprotic organic solvent;

(ii) at least one conducting salt;

(iii) at least one compound of formula (I)

-   -   wherein    -   X¹ and X² are independently from each other selected from N(R¹),        N═C(R²)—, P(R¹), O, and S;    -   R¹ is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,        C₂-C₁₀ alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇        (hetero)aryl, C₇-C₁₃ aralkyl, OR³, C(O)R³, C(NR³)R⁴, and        C(O)OR³, wherein alkyl, (hetero)cycloalkyl, alkenyl,        (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may be        substituted by one or more substituents selected from F, CN,        C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇        (hetero)aryl, S(O)₂OR^(3a), OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a),        C(O)R^(3a), C(O)OR^(3a), NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b);    -   R² is selected from H, CN, F, C₁-C₁₀ alkyl, C₃-C₆        (hetero)cycloalkyl, C₂-C₁₀ alkenyl, C₃-C₆ (hetero)cycloalkenyl,        C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃ aralkyl, S(O)₂OR³,        OS(O)₂R³, S(O)₂R³, OR³, C(O)R³, C(NR³)R⁴, C(O)OR³, NR³R⁴,        NC(O)R³, P(O)R³R⁴, and SiR³R⁴R⁵, wherein alkyl,        (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,        (hetero)aryl, and aralkyl may be substituted by one or more        substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆        (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl,        S(O)₂OR^(3a), OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a), C(O)R^(3a),        C(O)OR^(3a), NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b);    -   R³, R⁴, R⁵, R^(3a), and R^(3b) are independently from each other        selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀        alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇        (hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl,        (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,        (hetero)aryl, and aralkyl may be substituted by one or more        substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆        (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl,        S(O)₂OR^(3c), OS(O)₂R^(3c), S(O)₂R^(3c), OR^(3c), C(O)R^(3c),        C(O)OR^(3c), NR^(3c)R^(3d), and NC(O)R^(3c)R^(3d);    -   R^(3c) and R^(3d) are selected independently from each other        from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl,        and C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl,        alkenyl, and (hetero)aryl may be substituted by one or more        substituents selected from F and CN;    -   A¹ is selected from C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,        C₂-C₁₀ alkenyl, C₃-C₆ (hetereo)cycloalkenyl, C₂-C₆ alkynyl,        C₅-C₇ (hetero)aryl, C₇-C₁₃ aralkyl, OR⁶, C(O)R⁶, C(NR⁶)R⁷ and        C(O)OR⁶, wherein alkyl, (hetero)cycloalkyl, alkenyl,        (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may be        substituted by one or more substituents selected from F, CN,        C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇        (hetero)aryl, S(O)₂OR^(6a), OS(O)₂R^(6a), S(O)₂R^(6a), OR^(6a),        C(O)OR^(6a), NR^(6a)R^(6b), and NC(O)R^(6a)R^(6b);    -   A² is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,        C₂-C₁₀ alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇        (hetero)aryl, C₇-C₁₃ aralkyl, OR⁶, C(O)R⁶, C(NR⁶)R⁷ and C(O)OR⁶,        wherein alkyl, (hetero)cycloalkyl, alkenyl,        (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may be        substituted by one or more substituents selected from F, CN,        C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇        (hetero)aryl, S(O)₂OR^(6a), OS(O)₂R^(6a), S(O)₂R^(6a), OR^(6a),        C(O)OR^(6a), NR^(6a)R^(6b), and NC(O)R^(6a)R^(6b) with the        proviso that in case of X² is O or S, A² is neither H nor OR⁶;    -   R⁶, R⁷, R^(6a), and R^(6b) are independently from each other        selected from H, C₁-C₁₀ alkyl, C₅-C₆ (hetero)cycloalkyl, C₂-C₁₀        alkenyl, C₃-C₆ (hetereo)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇        (hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl,        (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,        (hetero)aryl, and aralkyl may be substituted by one or more        substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆        (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl,        S(O)₂OR^(6c), OS(O)₂R^(6c), S(O)₂R^(6c), OR^(6c), C(O)R^(6c),        C(O)OR^(6c), NR^(6c)R^(6d), and NC(O)R^(6c)R^(6d);    -   R^(6c) and R^(6d) are independently from each other selected        from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl,        and C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl,        alkenyl, and (hetero)aryl may be substituted by one or more        substituents selected from F and CN; and        (iv) optionally at least one further additive.

The problem is further solved by the use of at least one compound offormula (I) as additive for electrolytes in electrochemical cells; andby the electrochemical cell comprising the electrolyte composition (A)as described above, at least one cathode (B) comprising at least onecathode active material, and at least one anode (C) comprising at leastone anode active material.

The addition of at least one compound of general formula (I) to anelectrolyte for lithium ion secondary batteries comprising at least oneaprotic organic solvent or a mixture thereof and at least one conductingsalt leads to improved capacity retention of the lithium secondary ionbatteries.

The inventive electrolyte composition (A) is preferably liquid atworking conditions; more preferred it is liquid at 1 bar and 25° C.,even more preferred the electrolyte composition is liquid at 1 bar and−15° C., in particular the electrolyte composition is liquid at 1 barand −30° C., even more preferred the electrolyte composition is liquidat 1 bar and −50° C.

The electrolyte composition (A) contains at least one aprotic organicsolvent (i), preferably at least two aprotic organic solvents (i).According to one embodiment the electrolyte composition (A) may containup to ten aprotic organic solvents (i).

The at least one aprotic organic solvent (i) is preferably selected from

(a) cyclic and noncyclic organic carbonates, which may be partlyhalogenated,

(b) di-C₁-C₁₀-alkylethers, which may be partly halogenated,

(c) di-C₁-C₄-alkyl-C₂-C₆-alkylene ethers and polyethers, which may bepartly halogenated,

(d) cyclic ethers, which may be partly halogenated,

(e) cyclic and acyclic acetals and ketals, which may be partlyhalogenated,

(f) orthocarboxylic acids esters, which may be partly halogenated,

(g) cyclic and noncyclic esters of carboxylic acids, which may be partlyhalogenated,

(h) cyclic and noncyclic sulfones, which may be partly halogenated,

(i) cyclic and noncyclic nitriles and dinitriles, which may be partlyhalogenated, and

(j) ionic liquids, which may be partly halogenated.

More preferred the at least one aprotic organic solvent (i) is selectedfrom cyclic and noncyclic organic carbonates (a), di-C₁-C₁₀-alkylethers(b), di-C₁-C₄-alkyl-C₂-C₆-alkylene ethers and polyethers (c) and cyclicand acyclic acetals and ketals (e), even more preferred electrolytecomposition (A) contains at least one aprotic organic solvent (i)selected from cyclic and noncyclic organic carbonates (a) and mostpreferred electrolyte composition (A) contains at least two aproticorganic solvents (i) selected from cyclic and noncyclic organiccarbonates (a), in particular preferred electrolyte composition (A)contains at least one aprotic solvent (i) selected from cyclic organiccarbonates and at least one aprotic organic solvent (i) selected fromnoncyclic organic carbonates.

The aprotic organic solvents (a) to (j) may be partly halogenated, e.g.they may be partly fluorinated, partly chlorinated or partly brominated,preferably they may be partly fluorinated. “Partly halogenated” means,that one or more H of the respective molecule is substituted by ahalogen atom, e.g. by F, Cl or Br. Preference is given to thesubstitution by F. The at least one solvent (i) may be selected frompartly halogenated and non-halogenated aprotic organic solvents (a) to(j), i.e. the electrolyte composition may contain a mixture of partlyhalogenated and non-halogenated aprotic organic solvents.

Examples of suitable organic carbonates (a) are cyclic organiccarbonates according to the general formula (a1), (a2) or (a3)

whereinR^(a), R^(b) and R^(c) being different or equal and being independentlyfrom each other selected from hydrogen; C₁-C₄-alkyl, preferably methyl;F; and C₁-C₄-alkyl substituted by one or more F, e.g. CF₃.“C₁-C₄-alkyl” is intended to include methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec.-butyl and tert.-butyl.

Preferred cyclic organic carbonates (a) are of general formula (a1),(a2) or (a3) wherein R^(a), R^(b) and R^(c) are H. Examples are ethylenecarbonate, vinylene carbonate, and propylene carbonate. A preferredcyclic organic carbonate (a) is ethylene carbonate. Further preferredcyclic organic carbonates (a) are difluoroethylene carbonate (a4) andmonofluoroethylene carbonate (a5)

Examples of suitable non-cyclic organic carbonates (a) are dimethylcarbonate, diethyl carbonate, methylethyl carbonate and mixturesthereof.

In one embodiment of the invention the electrolyte composition (A)contains mixtures of non-cyclic organic carbonates (a) and cyclicorganic carbonates (a) at a ratio by weight of from 1:10 to 10:1,preferred of from 3:1 to 1:3.

Examples of suitable non-cyclic di-C₁-C₁₀-alkylethers (b) aredimethylether, ethylmethylether, diethylether, diisopropylether, anddi-n-butylether.

Examples of di-C₁-C₄-alkyl-C₂-C₆-alkylene ethers (c) are1,2-dimethoxyethane, 1,2-diethoxyethane, diglyme (diethylene glycoldimethyl ether), triglyme (triethylenglycol dimethyl ether), tetraglyme(tetraethylenglycol dimethyl ether), and diethylenglycoldiethylether.

Examples of suitable polyethers (c) are polyalkylene glycols, preferablypoly-C₁-C₄-alkylene glycols and especially polyethylene glycols.Polyethylene glycols may comprise up to 20 mol % of one or moreC₁-C₄-alkylene glycols in copolymerized form. Polyalkylene glycols arepreferably dimethyl- or diethyl-end capped polyalkylene glycols. Themolecular weight M_(w) of suitable polyalkylene glycols and especiallyof suitable polyethylene glycols may be at least 400 g/mol. Themolecular weight M_(w) of suitable polyalkylene glycols and especiallyof suitable polyethylene glycols may be up to 5 000 000 g/mol,preferably up to 2 000 000 g/mol.

Examples of suitable cyclic ethers (d) are tetrahydrofurane and1,4-dioxane.

Examples of suitable non-cyclic acetals (e) are 1,1-dimethoxymethane and1,1-diethoxymethane. Examples for suitable cyclic acetals (e) are1,3-dioxane and 1,3-dioxolane.

Examples of suitable orthocarboxylic acids esters (f) are tri-C₁-C₄alkoxy methane, in particular trimethoxymethane and triethoxymethane.

Examples of suitable noncyclic esters of carboxylic acids (g) are ethylacetate, methyl butanoate, and esters of dicarboxylic acids like1,3-dimethyl propanedioate. An example of a suitable cyclic ester ofcarboxylic acids (lactones) is γ-butyrolactone.

Examples of suitable cyclic and noncyclic sulfones (h) are ethyl methylsulfone and tetrahydrothiophene-1,1-dioxide.

Examples of suitable cyclic and noncyclic nitriles and dinitriles (i)are adiponitrile, acetonitrile, propionitrile, butyronitrile.

The water content of the inventive electrolyte composition is preferablybelow 100 ppm, based on the weight of the electrolyte composition, morepreferred below 50 ppm, most preferred below 30 ppm. The water contentmay be determined by titration according to Karl Fischer, e.g. describedin detail in DIN 51777 or ISO760: 1978.

The content of HF of the inventive electrolyte composition is preferablybelow 60 ppm, based on the weight of the electrolyte composition, morepreferred below 40 ppm, most preferred below 20 ppm. The HF content maybe determined by titration according to potentiometric orpotentiographic titration method.

The inventive electrolyte composition (A) furthermore contains at leastone conducting salt (ii). Electrolyte composition (A) functions as amedium that transfers ions participating in the electrochemical reactiontaking place in an electrochemical cell. The conducting salt(s) (ii)present in the electrolyte are usually solvated in the aprotic organicsolvent(s) (i). Preferably the conducting salt (ii) is a lithium salt.The conducting salt is preferably selected from the group consisting of

-   -   Li[F_(6-x)P(C_(y)F_(2y+1))_(x)], wherein x is an integer in the        range from 0 to 6 and y is an integer in the range from 1 to 20;    -   Li[B(R^(I))₄], Li[B(R^(I))²(OR^(II)O)] and Li[B(OR^(II)O)₂]        wherein each R^(I) is independently from each other selected        from F, Cl, Br, I, C₁-C₄ alkyl, C₂-C₄ alkenyl, and C₂-C₄        alkynyl, wherein alkyl, alkenyl, and alkynyl may be substituted        by one or more OR^(III), wherein R^(III) is selected from C₁-C₆        alkyl, C₂-C₆ alkenyl, and C₂-C₆ alkynyl, and    -   (OR^(II)O) is a bivalent group derived from a 1,2- or 1,3-diol,        a 1,2- or 1,3-dicarboxlic acid or a 1,2- or        1,3-hydroxycarboxylic acid, wherein the bivalent group forms a        5- or 6-membered cycle via the both oxygen atoms with the        central B-atom;    -   LiClO₄; LiAsF₆; LiCF₃SO₃; Li₂SiF₆; LiSbF₆; LiAlCl₄, lithium        tetrafluoro (oxalato) phosphate; lithium oxalate; and    -   salts of the general formula Li[Z(C_(n)F_(2n+1)SO₂)_(m)], where        m and n are defined as follows:    -   m=1 when Z is selected from oxygen and sulfur,    -   m=2 when Z is selected from nitrogen and phosphorus,    -   m=3 when Z is selected from carbon and silicon, and    -   n is an integer in the range from 1 to 20.

Suited 1,2- and 1,3-diols from which the bivalent group (OR^(II)O) isderived may be aliphatic or aromatic and may be selected, e.g., from1,2-dihydroxybenzene, propane-1,2-diol, butane-1,2-diol,propane-1,3-diol, butan-1,3-diol, cyclohexyl-trans-1,2-diol andnaphthalene-2,3-diol which are optionally are substituted by one or moreF and/or by at least one straight or branched non fluorinated, partlyfluorinated or fully fluorinated C₁-C₄ alkyl group. An example for such1,2- or 1,3-diole is 1,1,2,2-tetra(trifluoromethyl)-1,2-ethane diol.

“Fully fluorinated C₁-C₄ alkyl group” means, that all H-atoms of thealkyl group are substituted by F.

Suited 1,2- or 1,3-dicarboxlic acids from which the bivalent group(OR^(II)O) is derived may be aliphatic or aromatic, for example oxalicacid, malonic acid (propane-1,3-dicarboxylic acid), phthalic acid orisophthalic acid, preferred is oxalic acid. The 1,2- or 1,3-dicarboxlicacid are optionally substituted by one or more F and/or by at least onestraight or branched non fluorinated, partly fluorinated or fullyfluorinated C₁-C₄ alkyl group.

Suited 1,2- or 1,3-hydroxycarboxylic acids from which the bivalent group(OR^(II)O) is derived may be aliphatic or aromatic, for examplesalicylic acid, tetrahydro salicylic acid, malic acid, and 2-hydroxyacetic acid, which are optionally substituted by one or more F and/or byat least one straight or branched non fluorinated, partly fluorinated orfully fluorinated C₁-C₄ alkyl group. An example for such 1,2- or1,3-hydroxycarboxylic acids is 2,2-bis(trifluoromethyl)-2-hydroxy-aceticacid.

Examples of Li[B(R^(I))₄], Li[B(R^(I))₂(OR^(II)O)] and Li[B(OR^(II)O)₂]are LiBF₄, lithium difluoro oxalato borate and lithium dioxalato borate.

Preferably the at least one conducting salt (ii) is selected fromLiAsF₆, Li[N(FSO₂)₂], Li[N(CF₃SO₂)₂], LiClO₄, LiPF₆, LiBF₄, andLiPF₃(CF₂CF₃)₃, more preferred the conducting salt (ii) is selected fromLiPF₆ and LiBF₄, and the most preferred conducting salt (ii) is LiPF₆.

The at least one conducting salt (ii) is usually present at a minimumconcentration of at least 0.01 wt.-%, preferably of at least 1 wt.-%,and more preferred of at least 5 wt.-%, based on the total weight of theelectrolyte composition. Usually the upper concentration limit for theat least one conducting salt (ii) is 25 wt.-%, based on the total weightof the electrolyte composition.

The inventive electrolyte composition (A) contains as component (iii) atleast one compound of formula (I)

wherein

-   X¹ and X² are independently from each other selected from N(R¹),    N═C(R²), P(R¹), O, and S; preferably X¹ and X² are independently    from each other selected from N(R¹), N═C(R²) and O;-   R¹ is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆    alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, C₇-C₁₃ aralkyl, OR³, C(O)R³, C(NR³)R⁴, and C(O)OR³,    wherein alkyl, (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl,    alkynyl, (hetero)aryl, and aralkyl may be substituted by one or more    substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆    (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3a),    OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a), C(O)R^(3a), C(O)OR^(3a),    NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b);-   R² is selected from H, CN, F, C₁₀-C₆ alkyl, C₃-C₆    (hetero)cycloalkyl, C₂-C₁₀ alkenyl, C₃-C₆ (hetero)cycloalkenyl,    C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃ aralkyl, S(O)₂OR³,    OS(O)₂R³, S(O)₂R³, OR³, C(O)R³, C(NR³)R⁴, C(O)OR³, NR³R⁴, NC(O)R³,    P(O)R³R⁴, and SiR³R⁴R⁵, wherein alkyl, (hetero)cycloalkyl, alkenyl,    (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may be    substituted by one or more substituents selected from F, CN, C₁-C₆    alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₆-C₇ (hetero)aryl,    S(O)₂OR^(3a), OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a), C(O)R^(3a),    C(O)OR^(3a), NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b);-   R³, R⁴, R⁵, R^(3a), and R^(3b) are selected independently from each    other from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀    alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl, (hetero)cycloalkyl,    alkenyl, (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl    may be substituted by one or more substituents selected from F, CN,    C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇    (hetero)aryl, S(O)₂OR^(3c), OS(O)₂R^(3c), S(O)₂R^(3c), OR^(3c),    C(O)R^(3c), C(O)OR^(3c), NR^(3c)R^(3d), and NC(O)R^(3c)R^(3d);-   R^(3c) and R^(3d) are selected independently from each other from H,    C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, and C₅-C₇    (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and    (hetero)aryl may be substituted by one or more substituents selected    from F and CN;-   A1 is selected from C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀    alkenyl, C₃-C₆ (hetereo)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, C₇-C₁₃ aralkyl, OR⁶, C(O)R⁶, C(NR⁶)R⁷ and C(O)OR⁶,    wherein alkyl, (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl,    alkynyl, (hetero)aryl, and aralkyl may be substituted by one or more    substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆    (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(6a),    OS(O)₂R^(6a), S(O)₂R^(6a), OR^(6a), C(O)OR^(6a), NR^(6a)R^(6b), and    NC(O)R^(6a)R^(6b);-   A² is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,    C₂-C₁₀ alkenyl, C₃-C₆ (hetereo)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, C₇-C₁₃ aralkyl, OR⁶, C(O)R⁶, C(NR⁶)R⁷ and C(O)OR⁶,    wherein alkyl, (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl,    alkynyl, (hetero)aryl, and aralkyl may be substituted by one or more    substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆    (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(6a),    OS(O)₂R^(6a), S(O)₂R^(6a), OR^(6a), C(O)OR^(6a), NR^(6a)R^(6b), and    NC(O)R^(6a)R^(6b) with the proviso that in case of X² is O or S, A²    is neither H nor OR⁶;-   R⁶, R⁷, R^(6a), and R^(6b) are independently from each other    selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀    alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl, (hetero)cycloalkyl,    alkenyl, (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl    may be substituted by one or more substituents selected from F, CN,    C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇    (hetero)aryl, S(O)₂OR^(6c), OS(O)₂R^(6c), S(O)₂R^(6c), OR^(6c),    C(O)R^(6c), C(O)OR^(6c), NR^(6c)R^(6d), and NC(O)R^(6c)R^(6d);-   R^(6c) and R^(6d) are independently from each other selected from H,    C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, and C₅-C₇    (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and    (hetero)aryl may be substituted by one or more substituents selected    from F and CN.

The term “C₁-C₁₀ alkyl” as used herein means a straight or branchedsaturated hydrocarbon group with 1 to 10 carbon atoms having one freevalence. Preferred examples of C₁-C₁₀ alkyl are C₁-C₆ alkyl and include,e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, n-pentyl, iso-pentyl, 2,2-dimethylpropyl, n-hexyl,iso-hexyl, 2-ethyl hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl,n-nonyl, n-decyl and the like. Preferred are C₁-C₄ alkyl groups and mostpreferred are 2-propyl, methyl and ethyl. C₁-C₁₀ alkyl may besubstituted by one or more groups or atoms selected from CN, F, OR⁶,and/or one or more non-adjacent C-atoms of C₁-C₁₀ alkyl may be replacedby oxygen or sulfur. Preferably, in C₁-C₁₀ alkyl no C atoms are replacedby oxygen or sulfur.

The term “C₃-C₆ (hetero)cycloalkyl” as used herein means a cyclicsaturated hydrocarbon group with 3 to 6 carbon atoms having one freevalence wherein one or more C-atoms may be replaced by N, O or S.Examples of C₃-C₆ cycloalkyl include cyclopropyl, cyclobutyl,cyclopentyl and cyclohexyl, preferred is cyclohexyl. Examples of C₃-C₆hetero cycloalkyl are oxiranyl and tetrahydrofuryl, preferred isoxiranyl.

The term “C₂-C₁₀ alkenyl” as used herein refers to an unsaturatedstraight or branched hydrocarbon group with 2 to 10 carbon atoms havingone free valence. Unsaturated means that the alkenyl group contains atleast one C═C double bond. Preferred examples of C₂-C₁₀ alkenyl areC₂-C₆ alkenyl including for example ethenyl (vinyl), 1-propenyl,2-propenyl, 1-n-butenyl, 2-n-butenyl, iso-butenyl, 1-pentenyl, 1-hexenyland the like. Preferred are C₂-C₄alkenyl groups and in particularethenyl and propenyl, the preferred propenyl is 1-propen-3-yl, alsocalled allyl.

The term “C₃-C₆ (hetero)cycloalkenyl” as used herein refers to a cyclicunsaturated hydrocarbon group with 3 to 6 carbon atoms having one freevalence wherein one or more C-atoms may be replaced by N, O or S.Unsaturated means that the cycloalkenyl contains at least one C═C doublebond. Examples of C₃-C₆ (hetero)cycloalkenyl are cyclopropen,cycolbuten, cyclopenten, and cyclohexen.

The term “C₂-C₆ alkynyl” as used herein refers to an unsaturatedstraight or branched hydrocarbon group with 2 to 6 carbon atoms havingone free valence, wherein the hydrocarbon group contains at least oneC—C triple bond. C₂-C₁₀ alkynyl includes for example ethynyl,1-propynyl, 2-propynyl, 1-n-butinyl, 2-n-butynyl, iso-butinyl,1-pentynyl, 1-hexynyl and the like. Preferred is C₂-C₄ alkynyl, inparticular propynyl. The preferred propenyl is 1-propyn-3-yl also calledpropargyl.

The term “C₅-C₇ (hetero)aryl” as used herein denotes an aromatic 5- to7-membered hydrocarbon cycle having one free valence, wherein one ormore C-atom may be replaced by N, O or S. An example of C₅-C₇ aryl isphenyl, examples of C₅-C₇ heteroaryl are pyrrolyl, furanyl, thiophenyl,pyridinyl, pyranyl, and thiopyranyl.

The term “C₇-C₁₃ aralkyl” as used herein denotes an aromatic 5- to7-membered hydrocarbon cycle substituted by one or more C₁-C₆ alkyl. TheC₇-C₁₃ aralkyl group contains in total 7 to 13 C-atoms and has one freevalence. The free valence may be located in the aromatic cycle or in aC₁-C₆ alkyl group, i.e. C₇-C₁₃ aralkyl group may be bound via thearomatic part or via the alkyl part of the group. Examples of C₇-C₁₃aralkyl are methylphenyl, 1,2-dimethylphenyl, 1,3-dimethylphenyl,1,4-dimethylphenyl, ethylphenyl, 2-propylphenyl, and the like.

The term “A¹ and A² are combined and form together with X¹ and X² andthe C═C double bond a 5- to 7-membered unsaturated or aromaticheterocycle” is intended to mean that the 5- to 7-membered unsaturatedor aromatic hydrocarbon cycle or heterocycle is formed by A¹, A²together with the double bond of general formula (I), i.e. the twoC-atoms of the double bond are 2 members of the 5- to 7-memberedunsaturated or aromatic heterocycle. The term “unsaturated or aromaticheterocycle” means an unsaturated or aromatic hydrocarbon cycle whereinat least two C-atoms of the cycle are substituted by N, O, P or S.

According to one embodiment of the present invention the at least onecompound of formula (I) is selected from compounds of formula (I)

wherein

X¹ and X² are independently from each other selected from N(R¹) andN═C(R²);

R¹ is selected from H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl,and C₇-C₁₃ aralkyl, wherein alkyl, alkenyl (hetero)aryl, and aralkyl maybe substituted by one or more substituents selected from F, CN, C₁-C₆alkyl, OR^(3a), C(O)R^(3a), C(O)OR^(3a), S(O)₂OR^(3a), and OS(O)₂R^(3a);R² is selected from H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl,C₇-C₁₃ aralkyl, and NR³R⁴, wherein alkyl, alkenyl (hetero)aryl, andaralkyl may be substituted by one or more substituents selected from F,CN, C₁-C₆ alkyl, OR^(3a), C(O)R^(3a), C(O)OR^(3a), S(O)₂OR^(3a), andOS(O)₂R^(3a);R³, R⁴, and R^(3a) is selected from H, C₁-C₆ alkyl, and C₂-C₆ alkenyl,wherein alkyl and alkenyl may be substituted by one or more substituentsselected from F and CN;A¹ is selected from C₁-C₆ alkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, andC₇-C₁₃ aralkyl, wherein alkyl, alkenyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from F, CN, C₁-C₆alkyl, C₂-C₆ alkenyl, OS(O)₂R^(6a) and OR^(6a);A² is selected from H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl,and C₇-C₁₃ aralkyl, wherein alkyl, alkenyl, (hetero)aryl, and aralkylmay be substituted by one or more substituents selected from F, CN,C₁-C₆ alkyl, C₂-C₆ alkenyl, OS(O)₂R^(6a) and OR^(6a),R^(6a) is selected from H, C₁-C₆ alkyl, and C₂-C₆ alkenyl, wherein alkyland alkenyl may be substituted by one or more substituents selected fromF, CN, and OR^(6c);R^(6c) is selected from H, C₁-C₆ alkyl, and C₂-C₆ alkenyl wherein alkyland alkenyl may be substituted by one or more substituents selected fromF and CN.

In the context of the present invention, N═C(R²) and N═C(R²)— are beingused interchangeably, and they each refer to the following structuralunit:

In one embodiment of the present invention, both X¹ and X² areindependently from each other selected from N(R¹), P(R¹), O, and S.

In one embodiment of the present invention, X¹ and X² are independentlyfrom each other selected from N(R¹), N═C(R²) and O.

According to a preferred embodiment of the present invention the atleast one compound of formula (I) is selected from compounds of formula(I)

wherein

-   X¹ and X² are selected independently from each other from N(R¹) and    N═C(R²)—, and-   A¹ and A² are independently from each other selected from C₁-C₆    alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₃-C₆    (hetereo)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃    aralkyl, OR⁶, C(O)R⁶, C(NR⁶)R⁷ and C(O)OR⁶, wherein alkyl,    (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,    (hetero)aryl, and aralkyl may be substituted by one or more    substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆    (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(6a),    OS(O)₂R^(6a), S(O)₂R^(6a), OR^(6a), C(O)OR^(6a), NR^(6a)R^(6b), and    NC(O)R^(6a)R^(6b); and    the further substituents are defined as above.

Within this embodiment it is preferred if R¹ and R² are selectedindependently from each other from H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₅-C₇(hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl, alkenyl (hetero)aryl,and aralkyl may be substituted by one or more substituents selected fromF, CN, C₁-C₆ alkyl, and OR^(3a);

R^(3a) is selected from H, C₁-C₆ alkyl, and C₂-C₆ alkenyl, wherein alkyland alkenyl may be substituted by one or more substituents selected fromF and CN;

A¹ and A² are selected independently from each other from C₁-C₆ alkyl,C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl,alkenyl, (hetero)aryl, and aralkyl may be substituted by one or moresubstituents selected from F, CN, C₁-C₆ alkyl, and OR^(6a);R^(6a) is selected from H, C₁-C₆ alkyl, wherein alkyl may be substitutedby one or more substituents selected from F and CN.

Within this embodiment R¹ is preferably H.

Within this embodiment it is further preferred if

X¹ is NH, and

X² is N(R¹) or N═C(R²).

In one embodiment of the present invention, X¹ is selected from N(R¹),P(R¹), oxygen and sulfur, and X² is N═C(R²). Even more preferably,compound of formula (I) is selected from compounds of formula (I a)wherein X¹ is N(R¹) and X² is N═C(R²),

wherein R⁹ is selected from H, C₅-C₇ (hetero)aryl and C₇-C₁₃ aralkyl,and R⁹ is selected from C₅-C₇ (hetero)aryl and C₇-C₁₃ aralkyl,wherein C₅-C₇ (hetero)aryl and C₇-C₁₃ aralkyl may be substituted by oneor more substituents selected from F, CN, C₁-C₆ alkyl, and OR^(6a).

In one embodiment of the present invention the at least one compound offormula (I) is selected from compounds of formula (I b) wherein X¹ andX² are N(R¹)

wherein R⁸ is selected from H, C₅-C₇ (hetero)aryl and C₇-C₁₃ aralkyl,and R⁹ is selected from C₅-C₇ (hetero)aryl and C₇-C₁₃ aralkyl,wherein C₅-C₇ (hetero)aryl and C₇-C₁₃ aralkyl may be substituted by oneor more substituents selected from F, CN, C₁-C₆ alkyl, and OR^(6a).

In formulae (I a) and (I b) as well as in formula (I), specific examplesof C₅-C₇ (hetero)aryl are phenyl, 2-pyridyl, 3-pyridyl, 4.pyridyl.Specific examples of C₇-C₁₃ aralkyl are benzyl, 2-phenylethyl, and1-phenylethyl. Specific examples of substituted C₅-C₇ (hetero)aryl are2-methylphenyl, para-tolyl, para-methoxyphenyl, para-cyanophenyl,4-fluorophenyl, 2,4-difluorophenyl, and 3,5-dimethylphenyl.

The concentration of the at least one compound of formula (I) in theinventive electrolyte composition (A) usually is 0.001 to 10 wt.-%,preferred 0.01 to 2 wt.-%, more preferred 0.01 to <1 wt.-%, mostpreferred 0.01 to 0.9 wt.-%, and in particular 0.01 to 0.75 wt.-% basedon the total weight of the electrolyte composition (A).

The electrolyte composition (A) may contain at least one furtheradditive (iv) which is selected from the group consisting of vinylenecarbonate and its derivatives, vinyl ethylene carbonate and itsderivatives, methyl ethylene carbonate and its derivatives, lithium(bisoxalato) borate, lithium difluoro (oxalato) borate, lithiumtetrafluoro (oxalato) phosphate, lithium oxalate, 2-vinyl pyridine,4-vinyl pyridine, cyclic exo-methylene carbonates, sultones, cyclic andacyclic sulfonates, cyclic and acyclic sulfites, cyclic and acyclicsulfinates, organic esters of inorganic acids, acyclic and cyclicalkanes having a boiling point at 1 bar of at least 36° C., and aromaticcompounds, optionally halogenated cyclic and acyclic sulfonylimides,optionally halogenated cyclic and acyclic phosphate esters, optionallyhalogenated cyclic and acyclic phosphines, optionally halogenated cyclicand acyclic phosphites including, optionally halogenated cyclic andacyclic phosphazenes, optionally halogenated cyclic and acyclicsilylamines, optionally halogenated cyclic and acyclic halogenatedesters, optionally halogenated cyclic and acyclic amides, optionallyhalogenated cyclic and acyclic anhydrides, ionic liquids, and optionallyhalogenated organic heterocycles. The additive (iv) is preferablyselected to be different from the compound selected as conducting salt(ii) present in the respective electrolyte composition (A). Preferablyadditive (iv) is also different from the at least one organic aproticsolvent (i) present in the respective electrolyte composition (A).

Preferred ionic liquids according to the present invention are selectedfrom ionic liquids of formula [K][L] in which:

[K] denotes a cation, preferably reduction-stable, selected from thecation groups of the general formulae (II) to (IX)

wherein

-   R denotes H, C₁- to C₆-alkyl, C₂- to C₆-alkenyl, and phenyl,    preferably methyl, ethyl, and propyl;-   R^(A) denotes —(CH₂)_(s)—O—C(O)—R, —(CH₂)_(s)—C(O)—OR,    —(CH₂)_(s)—S(O)₂—OR, —(CH₂)_(s)—O—S(O)₂—R, —(CH₂)_(s)—O—S(O)₂—OR,    —(CH₂)_(s)—O—C(O)—OR, —(CH₂)_(s)—HC═CH—R, —(CH₂)_(s)—CN,

-   -   wherein individual CH₂ groups may be replaced by O, S or NR and        s=1 to 8, preferably s=1 to 3;

-   X^(A) denotes CH₂, O, S or NR^(B);

-   R^(B) denotes H, C₁- to C₆-alkyl, C₂- to C₆-alkenyl, phenyl, and    —(CH₂)_(s)—CN with s=1 to 8, preferably s=1 to 3; preferably R^(B)    is methyl, ethyl, propyl or H;    and    [L] denotes an anion selected from the group BF₄ ⁻, PF₆ ⁻,    [B(C₂O₄)₂]⁻, [F₂B(C₂O₄)]⁻, [N(S(O)₂F)₂]⁻,    [F_(p)P(C_(q)F_(2q+1))_(6-p)]⁻, [N(S(O)₂C_(q)F_(2q+1))₂],    [(C_(q)F_(2q+1))₂P(O)O]⁻, [C_(q)F_(2q+1)P(O)O₂]²⁻,    [OC(O)C_(q)F_(2q+1)]⁻, [OS(O)₂C_(q)F_(2q+1)]⁻;    [N(C(O)C_(q)F_(2q+1))₂]⁻;    [N(C(O)C_(q)F_(2q+1))(S(O)₂C_(q)F_(2q+1))]⁻;    [N(C(O)C_(q)F_(2q+1))(C(O))F]⁻; [N(S(O)₂C_(q)F_(2q+1))(S(O)₂F)]⁻;    [C(C(O)C_(q)F_(2q+1))₃]⁻, and [C(S(O)₂C_(q)F_(2q+1))₃N(SO₂CF₃)₂]⁻,    wherein p is an integer in the range from 0 to 6 and q is an integer    in the range from 1 to 20, preferably q is an integer in the ranger    from 1 to 4.

Preferred ionic liquids for use as additive (iv) are ionic liquids offormula [K][L] in which [K] is selected from pyrrolidinium cations offormula (II) with X is CH₂ and s is an integer in the range of from 1 to3 and [L] is selected from the group consisting of BF₄ ⁻, PF₆,[B(C₂O₄)₂]⁻, [F₂B(C₂O₄)]⁻, [N(S(O)₂F)₂]⁻, [N(SO₂C₂F₅)₂ ²]⁻,[F₃P(C₂F₅)₃]⁻, and [F₃P(C₄F₉)₃]⁻.

If one or more further additives (iv) are present in the electrolytecomposition (A), the total concentration of further additives (iv) is atleast 0.001 wt.-%, preferred 0.005 to 5 wt.-% and most preferred 0.01 to2 wt.-%, based on the total weight of the electrolyte composition (A).

A further object of the present invention is the use of at least onecompound of formula (I) as defined above as additive for electrolytes inelectrochemical cells, preferably in lithium ion secondaryelectrochemical cells.

The compounds of general formula (I) are well-suited as film formingadditives in electrochemical cells. The film may be formed on the anodeand/or on the cathode. Preferably the compounds of general formula (I)are used as film forming additives in lithium ion secondaryelectrochemical cells, in particular as additives forming a film on thecathode of lithium ion secondary electrochemical cells.

The compounds of general formula (I) are usually added to theelectrolyte composition to yield a concentration of from is 0.001 to 10wt.-%, preferred 0.01 to 2 wt.-%, more preferred 0.01 to <1 wt.-%, mostpreferred 0.01 to 0.9 wt.-%, and in particular 0.01 to 0.75 wt.-%, basedon the total weight of the electrolyte composition (A).

Another object of the present invention is an electrochemical cellcomprising

(A) the electrolyte composition as described above,

(B) at least one cathode comprising at least one cathode activematerial, and

(C) at least one anode comprising at least one anode active material.

Preferably the electrochemical cell is a secondary lithium ionelectrochemical cell, i.e. secondary lithium ion electrochemical cellcomprising a cathode comprising a cathode active material that canreversibly occlude and release lithium ions and an anode comprising aanode active material that can reversibly occlude and release lithiumions. The terms “secondary lithium ion electrochemical cell” and“(secondary) lithium ion battery” are used interchangeably within thepresent invention.

The at least one cathode active material preferably comprises a materialcapable of occluding and releasing lithium ions selected from lithiatedtransition metal phosphates and lithium ion intercalating transitionmetal oxides.

Examples of lithiated transition metal phosphates are LiFePO₄ andLiCoPO₄, examples of lithium ion intercalating transition metal oxidesare transition metal oxides with layer structure having the generalformula (X) Li_((1+z))[Ni_(a)Co_(b)Mn_(c)]_((1−z))O_(2+e) wherein z is 0to 0.3; a, b and c may be same or different and are independently 0 to0.8 wherein a+b+c=1; and −0.1≦e≦0.1, and manganese-containing spinels ofgeneral formula (XI) Li_(1+t)M_(2−t)O_(4−d) wherein d is 0 to 0.4, t is0 to 0.4 and M is Mn and at least one further metal selected from thegroup consisting of Co and Ni, andLi_((1+g))[Ni_(h)Co_(i)Al_(j)]_((1−g))O_(2+k). Typical values for g, h,l, j and k are: g=0, h=0.8 to 0.85, i=0.15 to 0.20, j=0.02 to 0.03 andk=0.

In one preferred embodiment the cathode active material is selected fromLiCoPO₄. The cathode containing LiCoPO₄ as cathode active material mayalso be referred to as LiCoPO₄ cathode. The LiCoPO₄ may be doped withFe, Mn, Ni, V, Mg, Al, Zr, Nb, Tl, Ti, K, Na, Ca, Si, Sn, Ge, Ga, B, As,Cr, Sr, or rare earth elements, i.e., a lanthanide, scandium andyttrium. LiCoPO₄ with olivine structure is particularly suited accordingthe present invention due to its high operating voltage (red-oxpotential of 4.8 V vs. Li/Li⁺), flat voltage profile and a hightheoretical capacity of about 170 mAh/g. The cathode may comprise aLiCoPO₄/C composite material. The preparation of a suited cathodecomprising a LiCoPO₄/C composite material is described in Scharabi etal., 2011 and Markevich et al., 2012.

In another preferred embodiment of the present invention the cathodeactive material is selected from transition metal oxides with layerstructure having the general formula (X)Li_((1+z))[Ni_(a)Co_(b)Mn_(c)]_((1−z))O_(2+e) wherein z is 0 to 0.3; a,b and c may be same or different and are independently 0 to 0.8 whereina+b+c=1; and −0.1≦e≦0.1. Preferred are transition metal oxides withlayer structure having the general formula (X)Li_((1+z))[Ni_(a)Co_(b)Mn_(c)]_((1−z))O_(2+e) wherein z is 0.05 to 0.3,a=0.2 to 0.5, b=0 to 0.3 and c=0.4 to 0.8 wherein a+b+c=1; and−0.1≦e≦0.1. In one embodiment of the present invention, the transitionmetal oxides with layer structure of general formula (X) are selectedfrom those in which [Ni_(a)Co_(b)Mn_(c)] is selected fromNi_(0.33)Co₀Mn_(0.66), Ni_(0.25)Co₀Mn_(0.75),Ni_(0.35)Co_(0.15)Mn_(0.5), Ni_(0.21)Co_(0.08)Mn_(0.71) andNi_(0.22)Co_(0.12)Mn_(0.66), in particular preferred areNi_(0.21)Co_(0.08)Mn_(0.71) and Ni_(0.22)Co_(0.12)Mn_(0.66). Thetransition metal oxides of general formula (X) are also called HighEnergy NCM (HE-NCM) since they have higher energy densities than usualNCMs. Both HE-NCM and NCM have operating voltage of about 3.3 to 3.8 Vagainst Li/Li⁺, but high cut off voltages (>4.6 V) have to be used forcharging HE-NCMS to actually accomplish full charging and to benefitfrom their higher energy density.

According to a further preferred embodiment of the present invention thecathode active material is selected from manganese-containing spinels ofgeneral formula (XI) Li_(1+t)M_(2−t)O_(4−d) wherein d is 0 to 0.4, t is0 to 0.4 and M is Mn and at least one further metal selected from thegroup consisting of Co and Ni. An example of a suitedmanganese-containing spinel of general formula (XI) isLiNi_(0.5)Mn_(1.5)O_(4−d). These spinels are also called HV (highvoltage)-spinels.

Many elements are ubiquitous. For example, sodium, potassium andchloride are detectable in certain very small proportions in virtuallyall inorganic materials. In the context of the present invention,proportions of less than 0.5% by weight of cations or anions aredisregarded, i.e. amounts of cations or anions below 0.5% by weight areregarded as non-significant. Any lithium ion-containing transition metaloxide comprising less than 0.5% by weight of sodium is thus consideredto be sodium-free in the context of the present invention.Correspondingly, any lithium ion-containing mixed transition metal oxidecomprising less than 0.5% by weight of sulfate ions is considered to besulfate-free in the context of the present invention.

The cathode may further comprise electrically conductive materials likeelectrically conductive carbon and usual components like binders.Compounds suited as electrically conductive materials and binders areknown to the person skilled in the art. For example, the cathode maycomprise carbon in a conductive polymorph, for example selected fromgraphite, carbon black, carbon nanotubes, carbon nanofibers, graphene ormixtures of at least two of the aforementioned substances. In addition,the cathode may comprise one or more binders, for example one or moreorganic polymers like polyethylene, polyacrylonitrile, polybutadiene,polypropylene, polystyrene, polyacrylates, polyvinyl alcohol,polyisoprene and copolymers of at least two comonomers selected fromethylene, propylene, styrene, (meth)acrylonitrile and 1,3-butadiene,especially styrene-butadiene copolymers, and halogenated (co)polymerslike polyvinlyidene chloride, polyvinly chloride, polyvinyl fluoride,polyvinylidene fluoride (PVdF), polytetrafluoroethylene, copolymers oftetrafluoroethylene and hexafluoropropylene, copolymers oftetrafluoroethylene and vinylidene fluoride and polyacrylnitrile.

Furthermore, the cathode may comprise a current collector which may be ametal wire, a metal grid, a metal web, a metal sheet, a metal foil or ametal plate. A suited metal foil is aluminum foil.

According to one embodiment of the present invention the cathode has athickness of from 25 to 200 μm, preferably of from 30 to 100 μm, basedon the whole thickness of the cathode without the thickness of thecurrent collector.

The anode (C) comprised within the lithium ion secondary battery of thepresent invention comprises an anode active material that can reversiblyocclude and release lithium ions. In particular carbonaceous materialthat can reversibly occlude and release lithium ions can be used asanode active material. Carbonaceous materials suited are crystallinecarbon such as a graphite material, more particularly, natural graphite,graphitized cokes, graphitized MCMB, and graphitized MPCF; amorphouscarbon such as coke, mesocarbon microbeads (MCMB) fired below 1500° C.,and mesophase pitch-based carbon fiber (MPCF); hard carbon and carbonicanode active material (thermally decomposed carbon, coke, graphite) suchas a carbon composite, combusted organic polymer, and carbon fiber.

Further anode active materials are lithium metal, or materialscontaining an element capable of forming an alloy with lithium.Non-limiting examples of materials containing an element capable offorming an alloy with lithium include a metal, a semimetal, or an alloythereof. It should be understood that the term “alloy” as used hereinrefers to both alloys of two or more metals as well as alloys of one ormore metals together with one or more semimetals. If an alloy hasmetallic properties as a whole, the alloy may contain a nonmetalelement. In the texture of the alloy, a solid solution, a eutectic(eutectic mixture), an intermetallic compound or two or more thereofcoexist. Examples of such metal or semimetal elements include, withoutbeing limited to, titanium (Ti), tin (Sn), lead (Pb), aluminum, indium(In), zinc (Zn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium(Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr) yttrium(Y), and silicon (Si). Metal and semimetal elements of Group 4 or 14 inthe long-form periodic table of the elements are preferable, andespecially preferable are titanium, silicon and tin, in particularsilicon. Examples of tin alloys include ones having, as a secondconstituent element other than tin, one or more elements selected fromthe group consisting of silicon, magnesium (Mg), nickel, copper, iron,cobalt, manganese, zinc, indium, silver, titanium (Ti), germanium,bismuth, antimony and chromium (Cr). Examples of silicon alloys includeones having, as a second constituent element other than silicon, one ormore elements selected from the group consisting of tin, magnesium,nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium,germanium, bismuth, antimony and chromium.

A further possible anode active material is silicon which is able totake up lithium ions. The silicon may be used in different forms, e.g.in the form of nanowires, nanotubes, nanoparticles, films, nanoporoussilicon or silicon nanotubes. The silicon may be deposited on a currentcollector. The current collector may be a metal wire, a metal grid, ametal web, a metal sheet, a metal foil or a metal plate. Preferred thecurrent collector is a metal foil, e.g. a copper foil. Thin films ofsilicon may be deposited on metal foils by any technique known to theperson skilled in the art, e.g. by sputtering techniques. Onepossibility of preparing Si thin film electrodes are described in R.Elazari et al.; Electrochem. Comm. 2012, 14, 21-24. It is also possibleto use a silicon/carbon composite as anode active material according tothe present invention.

Another possible anode active material are lithium ion intercalatingoxides of Ti.

Preferably the anode active material present in the inventive lithiumion secondary battery is selected from carbonaceous material that canreversibly occlude and release lithium ions, particularly preferred thecarbonaceous material that can reversibly occlude and release lithiumions is selected from crystalline carbon, hard carbon and amorphouscarbon, in particular preferred is graphite. In another preferredembodiment the anode active material present in the inventive lithiumion secondary battery is selected from silicon that can reversiblyocclude and release lithium ions, preferably the anode comprises a thinfilm of silicon or a silicon/carbon composite. In a further preferredembodiment the anode active material present in the inventive lithiumion secondary battery is selected from lithium ion intercalating oxidesof Ti.

The anode and cathode may be made by preparing an electrode slurrycomposition by dispersing the electrode active material, a binder,optionally a conductive material and a thickener, if desired, in asolvent and coating the slurry composition onto a current collector. Thecurrent collector may be a metal wire, a metal grid, a metal web, ametal sheet, a metal foil or a metal plate. Preferred the currentcollector is a metal foil, e.g. a copper foil or aluminum foil. Theinventive lithium ion batteries may contain further constituentscustomary per se, for example separators, housings, cable connectionsetc. The housing may be of any shape, for example cuboidal or in theshape of a cylinder, the shape of a prism or the housing used is ametal-plastic composite film processed as a pouch. Suited separators arefor example glass fiber separators and polymer-based separators likepolyolefin separators.

Several inventive lithium ion batteries may be combined with oneanother, for example in series connection or in parallel connection.Series connection is preferred. The present invention further providesfor the use of inventive lithium ion batteries as described above indevices, especially in mobile devices. Examples of mobile devices arevehicles, for example automobiles, bicycles, aircraft, or water vehiclessuch as boats or ships. Other examples of mobile devices are those whichare portable, for example computers, especially laptops, telephones orelectrical power tools, for example from the construction sector,especially drills, battery-driven screwdrivers or battery-drivenstaplers. But the inventive lithium ion batteries can also be used forstationary energy stores.

The invention is illustrated by the examples which follow, which do not,however, restrict the invention.

1. PREPARATION OF COMPOUNDS Compound 1:2-amino-3-(benzylideneamino)but-2-enedinitrile

To 1 L four necked bottle 54.05 g (0.50 mol) diaminomaleonitrile and 500ml methanol were added under nitrogen atmosphere. The mixture was heatedup to reflux temperature and 53.07 g (0.50 mol) benzaldehyde was addeddrop-wise within 30 minutes. The mixture was stirred at refluxtemperature for 24 hours. After cooling down to 10° C. the precipitatedsolid was filtered off and slurried in 200 ml of n-hexane. Afterstirring the suspension for 5 hours at room temperature, the brown solidwas filtered off giving 70 g (Yield: 71.35%)2-amino-3-(benzylideneamino)but-2-enedinitrile after drying 12 hours at40° C.

Compound 2: 2-amino-3-(p-tolylmethyleneamino)but-2-enedinitrile

To 250 ml four necked bottle 5.41 g (0.050 mol) diaminomaleonitrile, 50ml tetrahydrofuran and catalytic amount of sulfuric acid were addedunder nitrogen atmosphere. The mixture was heated up to refluxtemperature and 6.01 g (0.050 mol) 4-methylbenzaldehyde was addeddropwise within 10 minutes. The mixture was stirred at refluxtemperature for 10 hours. Following the evaporation of the solvent theyellow residual was twice slurried and washed in 200 ml n-hexane, givingby filtration 9.94 g (Yield: 94.55%)2-amino-3-(p-tolylmethyleneamino)but-2-enedinitrile after drying 6 hoursat 40° C.

Compound 3: 2-amino-3-(2-pyridilmethylenamino)but-2-enedinitrile

To 250 ml four necked bottle 5.41 g (0.050 mol) diaminomaleonitrile and50 ml methanol were added under nitrogen atmosphere. At room temperature5.36 g (0.050 mol) pyridine-2-carbaldehyde was added drop-wise within 5minutes. After stirring at room temperature for 15 minutes the mixturewas cooled down to 0° C. and the precipitated solid was filtered off.The solid was suspended in 100 ml of 1:1 mixture of n-hexane andmethyl-tertbutylether. After stirring the suspension for 1 hour at roomtemperature, the light yellow solid was filtered off giving 7.33 g(Yield: 74.33%) 2-amino-3-(2-pyridilmethylenamino)but-2-enedinitrileafter drying 6 hours at 40° C.

Compound 4: 2-amino-3-(benzylamino)but-2-enedinitrile

To 500 ml four necked bottle 10.0 g (0.051 mol)2-amino-3-(benzylideneamino)but-2-enedinitrile, 100 ml methanol and 150ml tetrahydrofuran were added under nitrogen atmosphere. At roomtemperature 1.93 g (0.051 mol) sodium borohydride was added portion-wisewithin 10 minutes. After stirring at room temperature for 15 minutes themixture was poured on 1 L ice-water and the precipitated solid wasfiltered off and washed with water. The filtered material was slurriedin 200 ml of n-hexane and after 2 hours stirring at room temperature,the light brown solid was filtered off giving 8.01 g (Yield: 80.90%)2-amino-3-(benzylamino)but-2-enedinitrile after drying 6 hours at 40° C.

Compound 5: 2-amino-3-(p-tolylmethylamino)but-2-enedinitrile

To 500 ml four necked bottle 10.56 g (0.050 mol)2-amino-3-(p-tolylmethyleneamino)but-2-enedinitrile, 100 ml methanol and150 ml tetrahydrofurane were added under nitrogen atmosphere. At roomtemperature 1.89 g (0.050 mol) sodium borohydride was added portion-wisewithin 10 minutes. After stirring at room temperature for 15 minutes themixture was poured on 1 L ice-water and the precipitated solid wasfiltered off and washed with water. The filtered material was slurriedin 400 ml of n-hexane and after 4 hours stirring at room temperature,the light brown solid was filtered off giving 9.87 g (Yield: 93.00%)2-amino-3-(p-tolylmethylamino)but-2-enedinitrile after drying 6 hours at40° C.

Compound 6: 2-(benzylamino)-3-(benzylideneamino)but-2-enedinitrile

To 250 ml four necked bottle 4.96 g (0.025 mol)2-amino-3-(benzylamino)but-2-enedinitrile, 50 ml methanol and catalyticamount of sulfuric acid were added under nitrogen atmosphere. Themixture was heated up to reflux temperature and 2.65 g (0.025 mol)benzaldehyde was added drop-wise within 5 minutes. The mixture wasstirred at reflux temperature for 24 hours. After cooling down to 0° C.the precipitated solid was filtered off and slurried in 200 ml ofn-hexane. After stirring the suspension for 5 hours at room temperature,the light green solid was filtered off giving 6.46 g (Yield: 90.25%)2-(benzylamino)-3-(benzylideneamino)but-2-enedinitrile after drying 12hours at 40° C.

Compound 7: 2,3-bis(benzylamino)but-2-enedinitrile

To 500 ml four necked bottle 14.63 g (0.051 mol)2-(benzylamino)-3-(benzylideneamino)but-2-enedinitrile, 100 ml methanoland 150 ml tetrahydrofurane were added under nitrogen atmosphere. Atroom temperature 1.93 g (0.051 mol) sodium borohydride was addedportion-wise within 10 minutes. After stirring at room temperature for15 minutes the mixture was poured on 1 L ice-water and the precipitatedsolid was filtered off and washed with water. The filtered material wasslurried in 400 ml of n-hexane and after 5 hours stirring at roomtemperature, the light brown solid was filtered off giving 12.22 g(Yield: 83.10%) 2,3-bis(benzylamino)but-2-enedinitrile after drying 6hours at 40° C.

Compound 8: Diaminomaleonitrile

Purchased from Aldrich

Compounds 1 to 9 are summarized in Table 1.

TABLE 1 Compound Name Structure 1 2-amino-3-(benzylideneamino)but-2-enedinitrile

2 2-amino-3-(p- tolylmethyleneamino) but-2-enedinitrile

3 2-amino-3-(2- pyridilmethylenamino) but-2-enedinitrile

4 2-amino-3-(benzylamino) but-2-enedinitrile

5 2-amino-3-(p- tolylmethylamino) but-2-enedinitrile

6 2-(benzylamino)-3- (benzylideneamino) but-2-enedinitrile

7 2,3-bis(benzylamino) but-2-enedinitrile

8 Diaminomaleonitrile

2. ELECTROCHEMICAL CELLS

Pouch type cells were used to prepare the electrochemical cells. A highvoltage spinel (LiNi_(0.5)Mn_(1.5)O₄, BASF SE) was used as cathodeactive material. A slurry composed of carbon black, graphite, binder andHV-spinel in N-ethyl-2-pyrrolidon (NEP) was prepared in a centrifuge.The slurry was spread onto an aluminum foil and the foil was then driedand cut to dimensions. The electrodes were inserted in a glove box underArgon atmosphere and dried at 120° C. in a vacuum oven. The anode was agraphite anode (Enertek, South Korea, Germany), and a glass fiberseparator was used (Whatman GF/A).

The basic electrolyte composition (LP57) contained a mixture of ethylenecarbonate and ethyl-methyl carbonate (3:7 by weight) as solvent and 12.7wt.-% of lithium hexafluorophosphate as conducting salt. The respectiveadditive was solved in the basic electrolyte composition. The amount ofelectrolyte composition used per cell was 105 μl.

The electrochemical testing was done in a Maccor potentiostat Serie 4000at 25° C. Cycling measurements were carried out up to an upper voltageof 4.8 V and to a lower voltage of 3.3 V. The first cycle was done at arate of C/10. A current of 1C was defined as 148 mA/g. A cycle iscomprised of one charge and one discharge step. The charge was carriedout in constant current constant voltage mode (CCCV). In this mode, aconstant current is passed through the electrochemical cell until a cellvoltage of 4.8 V was reached. The voltage is then held constant at 4.8 Vuntil the residual current falls to one tenth of its original value orif 30 min have elapsed. The discharge is performed in constant currentmode. A constant current was applied to the electrochemical cell until acell potential of 3.3 V was reached. The cycling program used is shownin Table 2. The steps listed under “Cycling” were repeated severaltimes, i.e. after finishing the 50 cycles at 1C, the cycling program wasrepeated starting with 3 cycles at 1 C, followed by 3 cycles at 2 C etc.The results of the cycling experiments are shown in Table 3.

TABLE 2 Cycling program Formation Cycling 0.1 C 0.5 C 1 C 2 C 4 C 10 C 1C Rest (14.8 mA/g) (74 mA/g) (148 mA/g) (296 mA/g) (592 mA/g) (1480mA/g) (148 mA/g) time 2 h Number 2 10 3 3 3 3 50 of cycles Performedonce Performed multiple times

TABLE 3 Discharge capacity at 1 C 1 C discharge capacity [%] Cycle # 1350 100 300 Comparative LP57 100.0 87.2 75.2 20.5 example 1 ComparativeLP57 + 0.1 wt.-% 97.4 88.9 77.8 22.2 example 2 Acrylonitrile ComparativeLP57 + 0.5 wt.-% 105 97.4 83 22.7 example 3 Acrylonitrile ComparativeLP57 + 2 wt.-% 90 72.7 50 5.5 example 4 Acrylonitrile Comparative LP57 +0.5 wt.-% 98.7 91.3 82.9 64.4 example 1 cpd 8 Inventive LP57 + 0.1 wt.-%99.1 93.2 87.2 71.8 example 2 cpd 4

The discharge capacity of the 13th cycle of the comparative example 1(LP 57, the basis electrolyte solution without any additive) was takenas basis value for all discharge capacities displayed in Table 3. It canbe seen that a small amount of acrylonitrile has a beneficial effect onthe discharge capacity, but that this effect is very small after 300cycles. The addition of diaminomaleonitrile (compound 8),2-amino-3-(benzylamino)but-2-enedinitrile (compound 4) or1,4,5,6-Tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile (compound 9)according to the invention results in a pronounced increase of thedischarge capacity even after 300 cycles in comparison to theelectrolyte composition containing the same amount of acrylonitrile.

The invention claimed is:
 1. An electrolyte composition (A) comprising:(i) an aprotic organic solvent; (ii) a conducting salt; (iii) a compoundof formula (I)

wherein X¹ and X² are independently from each other selected from thegroup consisting of N(R¹), N═C(R²)—, and P(R¹); R¹ is selected from thegroup consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl,C₇-C₃ aralkyl, OR³, C(O)R³, C(NR³)R⁴, and C(O)OR³, wherein alkyl,(hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,(hetero)aryl, and aralkyl may be substituted by one or more substituentsselected from the group consisting of F, CN, C₁-C₆ alkyl, C₃-C₆(hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3a),OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a), C(O)R^(3a), C(O)OR^(3a),NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b); R² is selected from the groupconsisting of H, CN, F, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl,C₇-C₁₃ aralkyl, S(O)₂OR³, OS(O)₂R³, S(O)₂R³, OR³, C(O)R³, C(NR³)R⁴,C(O)OR³, NR³R⁴, NC(O)R³, P(O)R³R⁴, and SiR³R⁴R⁵, wherein alkyl,(hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,(hetero)aryl, and aralkyl may be substituted by one or more substituentsselected from the group consisting of F, CN, C₁-C₆ alkyl, C₃-C₆(hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3a),OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a), C(O)R^(3a), C(O)OR^(3a),NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b); R³, R⁴, R⁵, R^(3a), and R^(3b) areindependently from each other selected from the group consisting of H,C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, C₃-C₆(hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, and C₇-C₁₃aralkyl, wherein alkyl, (hetero)cycloalkyl, alkenyl,(hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3c), OS(O)₂R^(3c), S(O)₂R^(3c),OR^(3c), C(O)R^(3c), C(O)OR^(3c), NR^(3c)R^(3d), and NC(O)R^(3c)R^(3d);R^(3c) and R^(3d) are selected independently from each other from thegroup consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀alkenyl, and C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl,alkenyl, and (hetero)aryl may be substituted by one or more substituentsselected from the group consisting of F and CN; A¹ is selected from thegroup consisting of C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl,C₇-C₁₃ aralkyl, OR⁶, C(O)R⁶, C(NR⁶)R⁷ and C(O)OR⁶, wherein alkyl,(hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,(hetero)aryl, and aralkyl may be substituted by one or more substituentsselected from the group consisting of F, CN, C₁-C₆ alkyl, C₃-C₆(hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(6a),OS(O)₂R^(6a), S(O)₂R^(6a), OR, C(O)OR^(6a), NR^(6a)R^(6b), andNC(O)R^(6a)R^(6b); A² is selected from the group consisting of H, C₁-C₁₀alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, C₃-C₆(hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃ aralkyl,OR⁶, C(O)R⁶, C(NR⁶)R⁷ and C(O)OR⁶, wherein alkyl, (hetero)cycloalkyl,alkenyl, (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR⁶, OS(O)₂R^(6a), S(O)₂R^(6a),OR^(6a), C(O)OR^(6a), NR^(6a)R^(6b), and NC(O)R^(6a)R^(6b) with theproviso that in case of X² is O or S, A² is neither H nor OR⁶; R⁶, R⁷,R^(6a), and R^(6b) are independently from each other selected from thegroup consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl,and C₇-C₁₃ aralkyl, wherein alkyl, (hetero)cycloalkyl, alkenyl,(hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₃-C₇ (hetero)aryl, S(O)₂OR^(6c), OS(O)₂R^(6c), S(O)₂R^(6c),OR^(6c), C(O)R^(6c), C(O)OR^(6c), NR^(6c)R^(6d), and NC(O)R^(6c)R^(6d);R^(6c) and R^(6d) are independently from each other selected from thegroup consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, and C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl,alkenyl, and (hetero)aryl may be substituted by one or more substituentsselected from the group consisting of F and CN; and (iv) optionally, afurther additive.
 2. The electrolyte composition (A) according to claim1 wherein both X¹ and X² are independently from each other selected fromthe group consisting of N(R¹) and P(R¹).
 3. The electrolyte composition(A) according to claim 1, wherein the compound of formula (I) isselected from the group consisting of compounds of formula (I) whereinX¹ and X² are independently from each other selected from the groupconsisting of N(R¹) and N═C(R²).
 4. The electrolyte composition (A)according to claim 1, wherein the compound of formula (I) is selectedfrom the group consisting of compounds of formula (I a) wherein X¹ isN(R¹) and X² is N═C(R²),

wherein R⁸ is selected from the group consisting of H, C₅-C₇(hetero)aryl and C₇-C₁₃ aralkyl, and R⁹ is selected from the groupconsisting of C₅-C₇ (hetero)aryl and C₇-C₁₃ aralkyl, wherein C₅-C₇(hetero)aryl and C₇-C₁₃ aralkyl may be substituted by one or moresubstituents selected from the group consisting of F, CN, C₁-C₆ alkyl,and OR^(6a).
 5. The electrolyte composition (A) according to claim 1,wherein the compound of formula (I) is selected from the groupconsisting of compounds of formula (I b) wherein X¹ and X² are N(R¹)

wherein R⁸ is selected from the group consisting of H, C₅-C₇(hetero)aryl and C₇-C₁₃ aralkyl, and R⁹ is selected from the groupconsisting of C₅-C₇ (hetero)aryl and C₇-C₁₃ aralkyl, wherein C₅-C₇(hetero)aryl and C₇-C₁₃ aralkyl may be substituted by one or moresubstituents selected from the group consisting of F, CN, C₁-C₆ alkyl,and OR^(6a).
 6. The electrolyte composition (A) according to claim 1,wherein the aprotic organic solvent (i) is selected from the groupconsisting of: (a) a cyclic or a noncyclic organic carbonate, which maybe partly halogenated, (b) a di-C₁-C₁₀-alkylether, which may be partlyhalogenated, (c) a di-C₁-C₄-alkyl-C₂-C₆-alkylene ether or polyether,which may be partly halogenated, (d) a cyclic ether, which may be partlyhalogenated, (e) a cyclic or an acyclic acetal or ketal, which may bepartly halogenated, (f) an orthocarboxylic acid ester, which may bepartly halogenated, (g) a cyclic or a noncyclic ester of a carboxylicacid, which may be partly halogenated, (h) a cyclic or a noncyclicsulfone, which may be partly halogenated, (i) a cyclic or a noncyclicnitrile or dinitrile, which may be partly halogenated, and (j) an ionicliquid, which may be partly halogenated.
 7. The electrolyte composition(A) according to claim 1, wherein the electrolyte composition (A)comprises an aprotic organic solvent (i) that is a cyclic organiccarbonate and an aprotic organic solvent (i) that is a noncyclic organiccarbonate.
 8. The electrolyte composition (A) according to claim 1,wherein the conducting salt (ii) is selected from the group consistingof: Li[F_(6-x)P(C_(y)F_(2y+1))_(x)], wherein x is an integer in therange from 0 to 6 and y is an integer in the range from 1 to 20;Li[B(R^(I))₄], Li[B(R^(I))₂(OR^(II)O)] and Li[B(OR^(II)O)₂] wherein eachR^(I) is independently from each other selected from the groupconsisting of F, Cl, Br, I, C₁-C₄ alkyl, C₂-C₄ alkenyl, and C₂-C₄alkynyl, wherein alkyl, alkenyl, and alkynyl may be substituted by oneor more OR^(III), wherein R^(III) is selected from the group consistingof C₁-C₆ alkyl, C₂-C₆ alkenyl, and C₂-C₆ alkynyl, and (OR^(II)O) is abivalent group derived from a 1,2- or 1,3-diol, a 1,2- or1,3-dicarboxlic acid or a 1,2- or 1,3-hydroxycarboxylic acid, whereinthe bivalent group forms a 5- or 6-membered cycle via both oxygen atomswith the central B-atom; LiClO₄; LiAsF₆; LiCF₃SO₃; Li₂SiF₆; LiSbF₆;LiAlCl₄, lithium tetrafluoro (oxalato) phosphate; lithium oxalate; and asalt of formula Li[Z(C_(n)F_(2n+1)SO₂)_(m)], where m and n are definedas follows: m=1 when Z is selected from the group consisting of oxygenand sulfur, m=2 when Z is selected from the group consisting of nitrogenand phosphorus, m=3 when Z is selected from the group consisting ofcarbon and silicon, and n is an integer in the range from 1 to
 20. 9.The electrolyte composition (A) according to claim 1, wherein theelectrolyte composition (A) further comprises at least one additive (iv)which is selected from the group consisting of vinylene carbonate andits derivatives, vinyl ethylene carbonate and its derivatives, methylethylene carbonate and its derivatives, lithium (bisoxalato) borate,lithium difluoro (oxalato) borate, lithium tetrafluoro (oxalato)phosphate, lithium oxalate, 2-vinyl pyridine, 4-vinyl pyridine, cyclicexo-methylene carbonates, sultones, organic esters of inorganic acids,acyclic and cyclic alkanes having a boiling point at 1 bar of at least36° C., and aromatic compounds, optionally halogenated cyclic andacyclic sulfonylimides, optionally halogenated cyclic and acyclicphosphate esters, optionally halogenated cyclic and acyclic phosphines,optionally halogenated cyclic and acyclic phosphites, optionallyhalogenated cyclic and acyclic phosphazenes, optionally halogenatedcyclic and acyclic silylamines, optionally halogenated cyclic andacyclic halogenated esters, optionally halogenated cyclic and acyclicamides, optionally halogenated cyclic and acyclic anhydrides, ionicliquids, and optionally halogenated organic heterocycles.
 10. Theelectrolyte composition (A) according to claim 1, wherein theconcentration of the compound of formula (I) is 0.001 to 10 wt.-%, basedon the total weight of the electrolyte composition (A).
 11. Anelectrochemical cell comprising (A) the electrolyte compositionaccording to claim 1, (B) a cathode comprising a cathode activematerial, and (C) an anode comprising an anode active material.
 12. Theelectrochemical cell according to claim 11, wherein the electrochemicalcell is a secondary lithium ion battery.
 13. The electrochemical cellaccording to claim 11, wherein at least one cathode active materialcomprises a material capable of occluding and releasing lithium ionsselected from the group consisting of lithiated transition metalphosphates and lithium ion intercalating transition metal oxides. 14.The electrochemical cell according to claim 11, wherein the anode activematerial comprises a lithium ion intercalating material selected fromthe group consisting of lithium ion intercalating carbonaceous material,lithium ion intercalating oxides of Ti, and lithium ion uptakingsilicon.
 15. An electrolyte composition (A) comprising: (i) an aproticorganic solvent; (ii) a conducting salt; (iii) a compound of formula (I)

wherein X¹ is selected from N(R¹), P(R¹), oxygen, and sulfur; X² isN═C(R²); R¹ is selected from the group consisting of H, C₁-C₁₀ alkyl,C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, C₆-C₆ (hetero)cycloalkenyl,C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃ aralkyl, OR³, C(O)R³,C(NR³)R⁴, and C(O)OR³, wherein alkyl, (hetero)cycloalkyl, alkenyl,(hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3a), OS(O)₂R^(3a), S(O)₂R^(3a),OR^(3a), C(O)R^(3a), C(O)OR^(3a), NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b);R² is selected from the group consisting of H, CN, F, C₁-C₁₀ alkyl,C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, C₃-C₆ (hetero)cycloalkenyl,C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃ aralkyl, S(O)₂OR³, OS(O)₂R³,S(O)₂R³, OR³, C(O)R³, C(NR³)R⁴, C(O)OR³, NR³R⁴, NC(O)R³, P(O)R³R⁴, andSiR³R⁴R⁵, wherein alkyl, (hetero)cycloalkyl, alkenyl,(hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3a), OS(O)₂R^(3a), S(O)₂R^(3a),OR^(3a), C(O)R^(3a), C(O)OR^(3a), NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b);R³, R⁴, R⁵, R^(3a), and R^(3b) are independently from each otherselected from the group consisting of H, C₁-C₁₀ alkyl, C₃-C₆(hetero)cycloalkyl, C₂-C₁₀ alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆alkenyl, C₅-C₇ (hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl,(hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,(hetero)aryl, and aralkyl may be substituted by one or more substituentsselected from the group consisting of F, CN, C₁-C₆ alkyl, C₃-C₆(hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3c),OS(O)₂R^(3c), S(O)₂R^(3c), S(O)₂R^(3c), C(O)R^(3c), OR^(3c),C(O)OR^(3c), NR^(3c)R^(3d), and NC(O)R^(3c)R^(3d); R^(3c) and R^(3d) areselected independently from each other from the group consisting of H,C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, and C₅-C₇(hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and(hetero)aryl may be substituted by one or more substituents selectedfrom the group consisting of F and CN; A¹ is selected from the groupconsisting of C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl,C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃aralkyl, OR⁶, C(O)R⁶, C(NR⁶)R⁷ and C(O)OR⁶, wherein alkyl,(hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,(hetero)aryl, and aralkyl may be substituted by one or more substituentsselected from the group consisting of F, CN, C₁-C₆ alkyl, C₃-C₆(hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(6a),OS(O)₂R^(6a), S(O)₂R^(6a), OR^(6a), C(O)OR^(6a), NR^(6a)R^(6b), andNC(O)R^(6a)R^(6b); A² is selected from the group consisting of H, C₁-C₁₀alkyl, C₆-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, C₃-C₆(hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃ aralkyl,OR⁶, C(O)R⁶, C(NR⁶)R⁷ and C(OR⁶, wherein alkyl, (hetero)cycloalkyl,alkenyl, (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(6a), OS(O)₂R^(6a), S(O)₂R^(6a),OR^(6a), C(O)OR^(6a), NR^(6a)R^(6b), and NC(O)R^(6a)R^(6b) with theproviso that in case of X² is O or S, A² is neither H nor OR⁶; R⁶, R⁷,R^(6a), and R^(6b) are independently from each other selected from thegroup consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl,and C₇-C₁₃ aralkyl, wherein alkyl, (hetero)cycloalkyl, alkenyl,(hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₁-C₆alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(6c), OS(O)₂R^(6c), S(O)₂R^(6c),OR^(6c), C(O)R^(6c), C(O)OR^(6c), NR^(6c)R^(6d), and NC(O)R^(6c)R^(6d);R^(6c) and R^(6d) are independently from each other selected from thegroup consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₁-C₆alkenyl, and C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl,alkenyl, and (hetero)aryl may be substituted by one or more substituentsselected from the group consisting of F and CN; and (iv) optionally, afurther additive.
 16. The electrolyte composition (A) according to claim15, wherein the aprotic organic solvent (i) is selected from the groupconsisting of: (a) a cyclic or a noncyclic organic carbonate, which maybe partly halogenated, (b) a di-C₁-C₁₀-alkylether, which may be partlyhalogenated, (c) a di-C₁-C₄-alkyl-C₂-C₆-alkylene ether or polyether,which may be partly halogenated, (d) a cyclic ether, which may be partlyhalogenated, (e) a cyclic or an acyclic acetal or ketal, which may bepartly halogenated, (f) an orthocarboxylic acid ester, which may bepartly halogenated, (g) a cyclic or a noncyclic ester of a carboxylicacid, which may be partly halogenated, (h) a cyclic or a noncyclicsulfone, which may be partly halogenated, (i) a cyclic or a noncyclicnitrile or dinitrile, which may be partly halogenated, and (j) an ionicliquid, which may be partly halogenated.
 17. The electrolyte composition(A) according to claim 15, wherein the electrolyte composition (A)comprises an aprotic organic solvent (i) that is a cyclic organiccarbonate and an aprotic organic solvent (i) that is a noncyclic organiccarbonate.
 18. The electrolyte composition (A) according to claim 15,wherein the conducting salt (ii) is selected from the group consistingof: Li[F_(6-x)P(C_(y)F_(2y+1))_(x)], wherein x is an integer in therange from 0 to 6 and y is an integer in the range from 1 to 20;Li[B(R^(I))₄], Li[B(R^(I))₂(OR^(II)O)] and Li[B(OR^(II)O)₂] wherein eachR^(I) is independently from each other selected from the groupconsisting of F, Cl, Br, I, C₁-C₄ alkyl, C₂-C₄ alkenyl, and C₂-C₄alkynyl, wherein alkyl, alkenyl, and alkynyl may be substituted by oneor more OR^(III), wherein R^(III) is selected from the group consistingof C₁-C₆ alkyl, C₂-C₆ alkenyl, and C₂-C₆ alkynyl, and (OR^(II)O) is abivalent group derived from a 1,2- or 1,3-diol, a 1,2- or1,3-dicarboxlic acid or a 1,2- or 1,3-hydroxycarboxylic acid, whereinthe bivalent group forms a 5- or 6-membered cycle via both oxygen atomswith the central B-atom; LiClO₄; LiAsF₆; LiCF₃SO₃; Li₂SiF₆; LiSbF₆;LiAlCl₄, lithium tetrafluoro (oxalato) phosphate; lithium oxalate; and asalt of formula Li[Z(C_(n)F_(2n+1)SO₂)_(m)], where m and n are definedas follows: m=1 when Z is selected from the group consisting of oxygenand sulfur, m=2 when Z is selected from the group consisting of nitrogenand phosphorus, m=3 when Z is selected from the group consisting ofcarbon and silicon, and n is an integer in the range from 1 to
 20. 19.The electrolyte composition (A) according to claim 15, wherein theelectrolyte composition (A) further comprises at least one additive (iv)which is selected from the group consisting of vinylene carbonate andits derivatives, vinyl ethylene carbonate and its derivatives, methylethylene carbonate and its derivatives, lithium (bisoxalato) borate,lithium difluoro (oxalato) borate, lithium tetrafluoro (oxalato)phosphate, lithium oxalate, 2-vinyl pyridine, 4-vinyl pyridine, cyclicexo-methylene carbonates, sultones, organic esters of inorganic acids,acyclic and cyclic alkanes having a boiling point at 1 bar of at least36° C., and aromatic compounds, optionally halogenated cyclic andacyclic sulfonylimides, optionally halogenated cyclic and acyclicphosphate esters, optionally halogenated cyclic and acyclic phosphines,optionally halogenated cyclic and acyclic phosphites, optionallyhalogenated cyclic and acyclic phosphazenes, optionally halogenatedcyclic and acyclic silylamines, optionally halogenated cyclic andacyclic halogenated esters, optionally halogenated cyclic and acyclicamides, optionally halogenated cyclic and acyclic anhydrides, ionicliquids, and optionally halogenated organic heterocycles.
 20. Anelectrochemical cell comprising (A) the electrolyte compositionaccording to claim 15, (B) a cathode comprising a cathode activematerial, and (C) an anode comprising an anode active material.